Fungicidal compositions

ABSTRACT

A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A) and B) in a synergistically effective amount, wherein 
     component A) is a compound of formula I 
                         
wherein R 1  is difluoromethyl or trifluoromethyl; Y is —CHR 2 — or
 
                         
and R 2  is hydrogen or C 1 -C 6 alkyl; or a tautomer of such a compound; and
 
component B) is a compound selected from compounds known for their fungicidal and/or insecticidal activity, is particularly effective in controlling or preventing fungal diseases of useful plants.

This application is a Continuation in Part of application Ser. No.11/576,719 filed Apr. 5, 2007, still pending, which is the NationalStage of International Application No. PCT/EP2005/010755 filed Oct. 6,2005, which claims priority to GB 0422401.0 filed Oct. 8, 2004, thecontents of which are incorporated herein by reference.

The present invention relates to novel fungicidal compositions for thetreatment of phytopathogenic diseases of useful plants, especiallyphytopathogenic fungi, and to a method of controlling phytopathogenicdiseases on useful plants.

It is known from WO 04/35589 that certain tricyclic carboxamidederivatives have biological activity against phytopathogenic fungi. Onthe other hand various fungicidal compounds of different chemicalclasses are widely known as plant fungicides for application in variouscrops of cultivated plants. However, crop tolerance and activity againstphytopathogenic plant fungi do not always satisfy the needs ofagricultural practice in many incidents and aspects.

There is therefore proposed in accordance with the present invention amethod of controlling phytopathogenic diseases on useful plants or onpropagation material thereof, which comprises applying to the usefulplants, the locus thereof or propagation material thereof a combinationof components A) and B) in a synergistically effective amount, wherein

component A) is a compound of formula I

whereinR₁ is difluoromethyl or trifluoromethyl; Y is —CHR₂— or

and R₂ is hydrogen or C₁-C₆alkyl; or a tautomer of such a compound; andcomponent B) is a compound selected from the group consisting ofa strobilurin fungicide, such as azoxystrobin (47), dimoxystrobin (226),fluoxastrobin (382), kresoxim-methyl (485), metominostrobin (551),orysastrobin, picoxystrobin (647), pyraclostrobin (690), trifloxystrobin(832); and a compound of formula B-6

an azole fungicide, such as azaconazole (40), bromuconazole (96),cyproconazole (207), difenoconazole (247), diniconazole (267),diniconazole-M (267), epoxiconazole (298), fenbuconazole (329),fluquinconazole (386), flusilazole (393), flutriafol (397), hexaconazole(435), imazalil (449), imibenconazole (457), ipconazole (468),metconazole (525), myclobutanil (564), oxpoconazole (607), pefurazoate(618), penconazole (619), prochloraz (659), propiconazole (675),prothioconazole (685), simeconazole (731), tebuconazole (761),tetraconazole (778), triadimefon (814), triadimenol (815), triflumizole(834), triticonazole (842), diclobutrazol (1068), etaconazole (1129),furconazole (1198), furconazole-cis (1199) and quinconazole (1378);a phenyl pyrrole fungicide, such as fenpiclonil (341) and fludioxonil(368);an anilino-pyrimidine fungicide, such as cyprodinil (208), mepanipyrim(508) and pyrimethanil (705);a morpholine fungicide, such as aldimorph, dodemorph (288),fenpropimorph (344), tridemorph (830), fenpropidin (343), spiroxamine(740); piperalin (648) and a compound of formula B-7

a compound of formula F-1

a compound of formula B-1

chlorothalonil (142); famoxadone (322); fenamidone (325); benalaxyl(56); benalaxyl-M; benomyl (62); bitertanol (84); boscalid (88);carboxin (120); carpropamid (122); copper (diverse salts); copperammoniumcarbonate; copper octanoate (170); copper oleate; coppersulphate (87; 172; 173); copper hydroxide (169); cyazofamid (185);cymoxanil (200); diethofencarb (245); dithianon (279); fenhexamide(334); fenoxycarb (340); fluazinam (363); flutolanil (396); folpet(400); guazatine (422); hymexazole; iprodione (470); lufenuron (490);mancozeb (496); metalaxyl (516); mefenoxam (517); metrafenone; nuarimol(587); paclobutrazol (612); pencycuron (620); penthiopyrad; procymidone(660); pyroquilon (710); quinoxyfen (715); silthiofam (729); sulfur(754); thiabendazole (790); thiram (804); triazoxide (821); tricyclazole(828); proquinazid (682); captan (114);a compound of formula B-2

a compound of formula B-3

a compound of formula B-4

a compound of formula B-8

a compound of formula B-9

a racemic compound of formula F-7 (trans)

a racemic compound of formula F-8 (cis)

a compound of formula F-9

which represents a mixture of racemic compounds of formula F-7 (trans)and F-8 (cis), wherein the ratio of racemic compounds of formula F-7(trans) to racemic compounds of formula F-8 (cis) is from 2:1 to 100:1;trinexapac-Ethyl (841); chlormequat chloride (137); ethephon (307);acibenzolar-5-methyl (6); mepiquat chloride (509);abamectin (1); emamectin benzoate (291); tefluthrin (769); thiamethoxam(792);a compound of formula A-1

a compound of formula A-2

a compound of formula A-3

a compound of formula A-4

a compound of formula A-5

a compound of formula A-6

a compound of formula A-7

a compound of formula A-8

a compound of formula A-9

a compound of formula A-10

a compound of formula A-11

a compound of formula A-12

a compound of formula A-13

a compound of formula A-14

a compound of formula A-15

a compound of formula A-15A

a compound of formula (A-16)

a compound of formula (A-17)

a compound of formula (A-18)

a compound of formula (A-19)

a compound of formula (A-20)

a compound of formula (A-21)

a compound of formula (A-22)

a compound of formula (A-23)

a compound of formula (A-24)

a compound of formula (A-25)

and a compound of formula (A-26)

It has now been found, surprisingly, that the active ingredient mixtureaccording to the invention not only brings about the additiveenhancement of the spectrum of action with respect to the phytopathogento be controlled that was in principle to be expected but achieves asynergistic effect which extends the range of action of the component(A) and of the component (B) in two ways. Firstly, the rates ofapplication of the component (A) and of the component (B) are loweredwhilst the action remains equally good. Secondly, the active ingredientmixture still achieves a high degree of phytopathogen control even wherethe two individual components have become totally ineffective in such alow application rate range. This allows, on the one hand, a substantialbroadening of the spectrum of phytopathogens that can be controlled and,on the other hand, increased safety in use.

However, besides the actual synergistic action with respect tofungicidal activity, the pesticidal compositions according to theinvention also have further surprising advantageous properties which canalso be described, in a wider sense, as synergistic activity. Examplesof such advantageous properties that may be mentioned are: a broadeningof the spectrum of fungicidal activity to other phytopathogens, forexample to resistant strains; a reduction in the rate of application ofthe active ingredients; synergistic activity against animal pests, suchas insects or representatives of the order Acarina; a broadening of thespectrum of pesticidal activity to other animal pests, for example toresistant animal pests; adequate pest control with the aid of thecompositions according to the invention, even at a rate of applicationat which the individual compounds are totally ineffective; advantageousbehaviour during formulation and/or upon application, for example upongrinding, sieving, emulsifying, dissolving or dispensing; increasedstorage stability; improved stability to light; more advantageuosdegradability; improved toxicological and/or ecotoxicological behaviour;improved characteristics of the useful plants including: emergence, cropyields, more developed root system, tillering increase, increase inplant height, bigger leaf blade, less dead basal leaves, strongertillers, greener leaf colour, less fertilizers needed, less seedsneeded, more productive tillers, earlier flowering, early grainmaturity, less plant verse (lodging), increased shoot growth, improvedplant vigor, and early germination; or any other advantages familiar toa person skilled in the art.

The alkyl groups appearing in the substituent definitions may bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl,hexyl and the branched isomers of pentyl and hexyl, preferred alkylgroups are methyl, isopropyl and tert-butyl, the most preferred alkylgroup is isopropyl.

The compounds of formula I occur in different stereoisomeric forms,which are described in formulae I_(I) and I_(II):

wherein R₁ and Y are as defined under formula I. The invention coversall such stereoisomers and mixtures thereof in any ratio.

Since compounds of formula I may also contain asymmetric carbon atoms inthe definition of the substituent Y, all the stereoisomers, all syn- andanti-forms and all chiral <R> and <S> forms are also included.

The components (B) are known. Where the components (B) are included in“The Pesticide Manual” [The Pesticide Manual—A World Compendium;Thirteenth Edition; Editor: C. D. S. Tomlin; The British Crop ProtectionCouncil], they are described therein under the entry number given inround brackets hereinabove for the particular component (B); forexample, the compound “abamectin” is described under entry number (1).Where “[CCN]” is added hereinabove to the particular component (B), thecomponent (B) in question is included in the “Compendium of PesticideCommon Names”, which is accessible on the internet [A. Wood; Compendiumof Pesticide Common Names, Copyright © 1995-2004]; for example, thecompound “acetoprole” is described under the internet addresshttp://www.alanwood.net/pesticides/acetoprole.html.

Most of the components (B) are referred to hereinabove by a so-called“common name”, the relevant “ISO common name” or another “common name”being used in individual cases. If the designation is not a “commonname”, the nature of the designation used instead is given in roundbrackets for the particular component (B); in that case, the IUPAC name,the IUPAC/Chemical Abstracts name, a “chemical name”, a “traditionalname”, a “compound name” or a “development code” is used or, if neitherone of those designations nor a “common name” is used, an “alternativename” is employed.

The following components B) are registered under a CAS-Reg. No.:aldimorph (CAS 91315-15-0); hymexazole (CAS 10004-44-1); copperAmmoniumcarbonate (CAS 33113-08-5); copper oleate (CAS 1120-44-1);benalaxyl-M (CAS 98243-83-5); metrafenone (CAS 220899-03-6) andpenthiopyrad (CAS 183675-82-3). The compounds of formulae F-7, F-8 andF-9 are described in WO 03/74491. The compounds of formulae A-1, A-2,A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15,A-18, A-19, A-20, A-21 and A-22 are described in WO 03/15519. Thecompound of formula A-15A is described in EP-A-1 006 107. The compoundsof formulae A-16, A-17, A-23, A-24, A-25 and A-26 are described in WO04/67528. The compound of formula F-1 is described in WO 01/87822.Compounds of formula B-1A and the compound of formula B-1 are describedin WO 98/46607. The compound of formula B-2 is described in WO 99/42447.The compound of formula B-3 is described in WO 96/19442. The compound offormula B-4 is described in WO 99/14187. The compound of formula B-5 isdescribed in U.S. Pat. No. 5,945,423 and WO 94/26722. The compound offormula B-6 is described in EP-0-936-213. The compound of formula B-7 isdescribed in U.S. Pat. No. 6,020,332, CN-1-167-568, CN-1-155-977 andEP-0-860-438. The compound of formula B-8 is registered under CAS-Reg.No.: 325156-49-8 and is also known as Pyribencarb. The compound offormula B-9 is registered under CAS-Reg. No.: 348635-87-0 and is alsoknown as Ambromdole or Amisulbrom.

According to the instant invention, a “racemic compound” means a mixtureof two enantiomers in a ratio of substantially 50:50 of the twoenantiomers.

Throughout this document the expression “combination” stands for thevarious combinations of components A) and B), for example in a single“ready-mix” form, in a combined spray mixture composed from separateformulations of the single active ingredient components, such as a“tank-mix”, and in a combined use of the single active ingredients whenapplied in a sequential manner, i.e. one after the other with areasonably short period, such as a few hours or days. The order ofapplying the components A) and B) is not essential for working thepresent invention.

The combinations according to the invention may also comprise more thanone of the active components B), if, for example, a broadening of thespectrum of phytopathogenic disease control is desired. For instance, itmay be advantageous in the agricultural practice to combine two or threecomponents B) with any of the compounds of formula I, or with anypreferred member of the group of compounds of formula I.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl or trifluoromethyl; Y is —CHR₂— and R₂ ishydrogen or C₁-C₆alkyl; and one component B) as described above.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is trifluoromethyl; and one component B) as described above.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and one component B) as described above.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and R₂ is C₁-C₆alkyl, and one component B)as described above.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl, Y is —CHR₂— and R₂ is isopropyl; and onecomponent B) as described above. Within this embodiment of the presentinvention compounds of formula I occur in different stereoisomericforms, which are described as the single enantiomers of formulaeI_(III), I_(IV), I_(V) and I_(VI):

The invention covers all such single enantiomers and mixtures thereof inany ratio.

The compounds of formula I and their manufacturing processes startingfrom known and commercially available compounds are described in WO04/035589. In particular it is described in WO 04/035589 that thepreferred compound of formula I, wherein R₁ is difluoromethyl, Y is—CHR₂— and R₂ is isopropyl, which is represented by the structure I^(a),

can be prepared by reacting an acid chloride of formula II

with an amine of formula III

Acids of formula IV

are used for the production of the acid chlorides of formula II, viareaction steps as described in WO 04/035589. When producing the acids ofthe formula IV using said methology impurities of formula IVA, IVBand/or IVC may be formed:

When applying the described manufacturing processes for compounds offormula I^(a), some/all of those impurities may be carried throughdifferent steps of said manufacturing processes. This then can lead tothe formation of the corresponding acid chlorides (IIA, IIB and/or IIC)

and to the formation of the corresponding amides (VA, VB and/or VC)

as further impurities of compounds of formula I^(a). The presence/amountof said impurities in preparations of said compounds of formula I^(a)varies dependent on purification steps used.

Amines of formula III_(B)

wherein R₁′ and R₂′ are both independently hydrogen or C₁-C₅alkyl, butR₁′ and R₂′ are both chosen in a way that the grouping —CHR₁′R₂′altogether is a C₁-C₆alkyl group. Said grouping —CHR₁′R₂′ represents apreferred definition of the substituent R₂ of compounds of formula I.

Said amines of formula III_(B) can be produced according to scheme 1.

9-Alkylidene-5-nitro-benzonorbornadienes of formula D′, wherein R₁′ andR₂′ are as defined for compounds of formula III_(B), can be synthesizedthrough Diels-Alder addition of an in situ generated benzyne B′ [forexample starting from a 6-nitroanthranilic acid of formula (A′) bydiazotation with i-amyl or t-butyl nitrite], as described by L. Paquetteet al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitableprecursors (see H. Pellissier et al. Tetrahedron, 59, 701 (2003), R.Muneyuki and H. Tanida, J. Org. Chem. 31, 1988 (1966)] to a 6-alkyl- or6,6-dialkylfulvene according to or by analogy to R. Muneyuki and H.Tanida, J. Org. Chem. 31, 1988 (1966), P. Knochel et al, Angew. Chem.116, 4464 (2004), J. W. Coe et al, Organic Letters 6, 1589 (2004), L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), R. N. Warrener etal. Molecules, 6, 353 (2001), R. N. Warrener et al. Molecules, 6, 194(2001).

Suitable aprotic solvents for this step are for example diethyl ether,butyl methyl ether, ethyl acetate, dichloromethane, acetone,tetrahydrofurane, toluene, 2-butanone or dimethoxyethane. Reactiontemperatures range from room temperature to 100° C., preferably 35-80°C. 6-Alkyl- or 6,6-dialkylfulvenes of formula C′ are available accordingto M. Neuenschwander et al, Helv. Chim. Acta, 54, 1037 (1971), ibid 48,955 (1965). R. D. Little et al, J. Org. Chem. 49, 1849 (1984), 1. Erdenet al, J. Org. Chem. 60, 813 (1995) and S. Collins et al, J. Org. Chem.55, 3395 (1990).

Anilines of formula E′ may be obtained according to scheme 2 by partialhydrogenolysis of D′, for example by interrupting H₂ uptake after 4equivalents. Suitable solvents include tetrahydrofurane, ethyl acetate,methanol, ethanol, toluene or benzene and others. Catalysts are forexample Ra/Ni, Rh/C or Pd/C. Pressure: atmospheric pressure or pressureup to 6 bar, preferentially atmospheric pressure. Temperatures rangefrom room temperature or up to 50° C., preferentially 20-30° C.

Anilines of formula III_(B) may be obtained from anilines of formula E′by hydrogenation. Suitable solvents are for example tetrahydrofurane,methanol, ethanol, toluene, dichloromethane, ethyl acetate. Preferredsolvents are tetrahydrofurane and methanol. Temperatures range from 10to 50° C., preferentially 20-30° C., more preferred room temperature.Pressure: atmospheric pressure to 150 bar, preferred is atmosphericpressure to 100 bar. The choice of catalyst influences thesyn/anti-ratio. Catalysts such as Rh/C, Rh/Al₂O₃, Rh₂O₃, Pt/C or PtO₂result in syn-enrichment (preferred Rh/C). Catalysts such as Ra/Ni,Ir(COD)Py(Pcy) or Pd/C result in anti-enrichment (preferred Pd/C).

Anilines of formula III_(B) may also be produced according to scheme 3.

Anilines III_(B) may be obtained by a one-pot reaction from compounds offormula D′ via exhaustive hydrogenation (scheme 3). Suitable solventsare for example tetrahydrofurane, methanol, ethanol, toluene or ethylacetate. Preferred solvents are tetrahydrofurane or methanol.Temperatures range from room temperature to 50° C., preferred is roomtemperature to 30° C., most preferred room temperature. Pressure:atmospheric pressure to 100 bar, more preferred 50 bar, even morepreferred 20 bar, most preferred atmospheric pressure to 4-6 bar.Likewise, as described for scheme 2 above, the choice of catalystinfluences the syn/anti-ratio. Catalysts such as Rh/C, Rh/Al₂O₃, Rh₂O₃,Pt/C or PtO₂ result in syn-enrichment. Catalysts such as Pd/C,Ir(COD)Py(Pcy) or Ra/Ni result in anti-enrichment (preferred catalyst isPd/C).

The following compounds of formula D′ are useful for manufacturingpreferred compounds of formula I.

TABLE 1 Compounds of formula D′ (D′)

Cpd No. R₁′ R₂′ Remarks Z1.01 H CH₃ E/Z-mixture Z1.02 H C₂H₅ E/Z-mixtureZ1.03 H n-C₃H₇ E/Z-mixture Z1.04 H i-C₃H₇ E/Z-mixture Z1.05 H c-C₃H₅E/Z-mixture Z1.06 H n-C₄H₉ E/Z-mixture Z1.07 H i-C₄H₉ E/Z-mixture Z1.08H sec-C₄H₉ E/Z-mixture Z1.09 H t-C₄H₉ E/Z-mixture Z1.10 H n-C₅H₁₁E/Z-mixture Z1.11 CH₃ CH₃ Z1.12 C₂H₅ C₂H₅ Z1.13 CH₃ C₂H₅ E/Z-mixtureZ1.14 CH₃ n-C₃H₇ E/Z-mixture Z1.15 CH₃ i-C₃H₇ E/Z-mixture Z1.16 CH₃c-C₃H₅ E/Z-mixture Z1.17 H H

The following compounds of formula E′ are useful for manufacturingpreferred compounds of formula I.

TABLE 2 Compounds of formula E′ (E′)

Cpd No. R₁′ R₂′ Remarks Z2.01 H CH₃ E/Z-mixture Z2.02 H C₂H₅ E/Z-mixtureZ2.03 H n-C₃H₇ E/Z-mixture Z2.04 H i-C₃H₇ E/Z-mixture Z2.05 H c-C₃H₅E/Z-mixture Z2.06 H n-C₄H₉ E/Z-mixture Z2.07 H i-C₄H₉ E/Z-mixture Z2.08H sec-C₄H₉ E/Z-mixture Z2.09 H t-C₄H₉ E/Z-mixture Z2.10 H n-C₅H₁₁E/Z-mixture Z2.11 CH₃ CH₃ Z2.12 C₂H₅ C₂H₅ Z2.13 CH₃ C₂H₅ E/Z-mixtureZ2.14 CH₃ n-C₃H₇ E/Z-mixture Z2.15 CH₃ i-C₃H₇ E/Z-mixture Z2.16 CH₃c-C₃H₅ E/Z-mixture Z2.17 H H

The following compounds of formula III_(B) are useful for manufacturingpreferred compounds of formula I.

TABLE 3 Compounds of formula III_(B) (III_(B))

Cpd No. R₁′ R₂′ Remarks Z3.01 H CH₃ syn/anti-mixture Z3.02 H C₂H₅syn/anti-mixture Z3.03 H n-C₃H₇ syn/anti-mixture Z3.04 H i-C₃H₇syn/anti-mixture Z3.05 H c-C₃H₅ syn/anti-mixture Z3.06 H n-C₄H₉syn/anti-mixture Z3.07 H i-C₄H₉ syn/anti-mixture Z3.08 H sec-C₄H₉syn/anti-mixture Z3.09 H t-C₄H₉ syn/anti-mixture Z3.10 H n-C₅H₁₁syn/anti-mixture Z3.11 CH₃ CH₃ syn/anti-mixture Z3.12 C₂H₅ C₂H₅syn/anti-mixture Z3.13 CH₃ C₂H₅ syn/anti-mixture Z3.14 CH₃ n-C₃H₇syn/anti-mixture Z3.15 CH₃ i-C₃H₇ syn/anti-mixture Z3.16 CH₃ c-C₃H₅syn/anti-mixture Z3.17 H H syn/anti-mixture

The following examples illustrate the production of compounds of formulaIII_(B).

a) Benzyne Adduct

EXAMPLE H1 9-Isopropylidene-5-nitro-benzonorbornadiene (Cpd No. Z1.11)

A mixture of 6-nitroanthranilic acid (110.4 g, 0.6 mol) and6,6-dimethylfulvene (98.5 g, 1.5 eq.) in 700 ml dimethoxyethane wasadded dropwise to a solution of t-butyl nitrite (96.3 g, 1.4 eq.) in 2liter 1,2-dimethoxyethane under N₂-atmosphere at 72° C. within 20minutes. A vigorous formation of gas started immediately and thetemperature rose to 79° C. Gas formation ceased after 30 min. After 3 hat reflux temperature the mixture was cooled to room temperature,evaporated and purified on silica gel in hexane-ethyl acetate 95:5resulting in 76.7 g of 9-isopropylidene-5-nitro-benzonorbornadiene as ayellow solid (m.p. 94-95° C.). ¹H-NMR (CDCl3), ppm: 7.70 (d, 1H), 7.43(d, 1H), 7.06 (t, 1H), 6.99 (m, 2H), 5.34 (brd s, 1H), 4.47 (brd s, 1H),1.57 (2 d, 6H). ¹³C-NMR (CDCl₃), ppm: 159.83, 154.30, 147.33, 144.12,142.89, 141.93, 125.23 (2×), 119.32, 105.68, 50.51, 50.44, 19.05, 18.90.

b) Two-Step Hydrogenation

EXAMPLE H2 9-Isopropylidene-5-amino-benzonorbornene (Cpd No. Z2.11)

5.0 g 9-isopropylidene-5-nitro-benzonorbornadiene (Cpd No. Z1.11) (22mmol) were hydrogenated in 50 ml tetrahydrofurane in the presence of 1.5g 5% Rh/C at 25° C. and atmospheric pressure. After uptake of 4equivalents of hydrogen (2.01 liter or 102% of theory) the mixture wasfiltered, evaporated and purified on silica gel in hexane-ethylacetate-6:1 giving 2.76 g 9-isopropylidene-5-amino-benzonorbornene as asolid (m.p. 81-82° C.; yield: 62.9% of theory). ¹H-NMR (CDCl3), ppm:6.90 (t, 1H), 6.67 (d, 1H), 6.46 (d, 1H), 3.77 (m, 1H), 3.73 (m, 1H),3.35 (brd, exchangeable with D₂O, 2H), 1.89 (m, 2H), 1.63 (2 s, 6H),1.26 (m, 2H). ¹³C-NMR (CDCl₃), ppm: 148.73, 147.65, 138.30, 131.75,126.19, 113.12, 110.89, 110.19, 43.97, 39.44, 26.98, 26.06, 19.85,19.75.

EXAMPLE H3 9-Isopropyl-5-amino-benzonorbornene (Cpd No. Z3.11)

200 mg 9-isopropylidene-5-amino-benzonorbornene (Cpd No. Z2.11) werehydrogenated in the presence of 100 mg 5% Rh/C in 40 ml tetrahydrofuranein a stainless steel autoclave at room temperature at 100 bar resultingin 9-isopropyl-5-amino-benzonorbornene in the form of an oil(syn/anti-ratio 9:1). syn-Epimer: ¹H-NMR (CDCl₃), ppm: 6.91 (t, 1H),6.64 (d, 1H), 6.48 (d, 1H), 3.54 (brd, exchangeable with D₂O, 2H), 3.20(m, 1H), 3.15 (m, 1H), 1.92 (m, 2H), 1.53 (d, 1H), 1.18 (m, 2H), 1.02(m, 1H), 0.81 (m, 6H); ¹³C-NMR (CDCl3), ppm: 147.73, 140.03, 130.15,126.41, 113.35, 112.68, 69.00, 46.62, 42.06, 27.74, 26.83, 25.45, 22.32,22.04; anti-epimer: ¹H-NMR (CDCl₃), ppm: 6.89 (t, 1H), 6.63 (d, 1H),6.46 (d, 1H), 3.55 (brd, exchangeable with D₂O, 2H), 3.16 (m, 1H), 3.13(m, 1H), 1.87 (m, 2H), 1.48 (d, 1H), 1.42 (m, 1H), 1.12 (m, 2H), 0.90(m, 6H); ¹³C-NMR (CDCl₃), ppm: 150.72, 138.74, 133.63, 126.15, 112.94,111.53, 68.05, 45.21, 40.61, 26.25, 24.47, 23.55, 20.91 (2×).Assignments were made on the basis of NOE-NMR-experiments.

c) One-Pot Hydrogenation:

EXAMPLE H4 9-Isopropyl-5-amino-benzonorbornene (Cpd No. Z3.11)syn-enrichment

35.9 g 9-isopropylidene-5-nitro-benzonorbornadiene (Cpd No. Z1.11) in400 ml tetrahydrofurane were exhaustively hydrogenated in the presenceof 25 g 5% Rh/C over 106 h. Filtration and evaporation of the solventresulted in 32.15 g 9-isopropyl-5-amino-benzonorbornene (Cpd No. Z3.11)in the form of an oil (syn/anti-ratio 9:1; yield: 97.4% of theory). NMRdata: see above.

EXAMPLE H5 9-Isopropyl-5-amino-benzonorbornene (Cpd No. Z3.11):anti-enrichment

41.41 g 9-isopropylidene-5-nitro-benzonorbornadiene (Cpd No. Z10.11) in1 liter tetrahydrofurane were exhaustively hydrogenated for four hoursin the presence of 22 g 5% Pd/C at room temperature and atmosphericpressure. Filtration and evaporation followed by purification on silicagel in hexane-ethyl acetate-7:1 gave 29.91 g9-isopropyl-5-amino-benzonorbornene (Cpd No. Z3.11) (syn/anti-ratio 3:7;yield: 81.5%) in the form of an oil. NMR data: see above.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of formula Ia(syn)

which represents a single enantiomer of formula I_(III), a singleenantiomer of formula I_(IV) or a mixture in any ratio of the singleenantiomers of formulae I_(III) and I_(IV); and one component B) asdescribed above.

Among this embodiment of the invention preference is given to thosecombinations which comprise as component A) a racemic compound of theformula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV); and one component B) asdescribed above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ib (anti)

which represents a single enantiomer of formula I_(V), a singleenantiomer of formula I_(VI) or a mixture in any ratio of the singleenantiomers of formulae I_(V) and I_(VI); and one component B) asdescribed above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a racemic compoundof the formula Ib (anti), which represents a racemic mixture of thesingle enantiomers of formulae I_(V) and I_(VI); and one component B) asdescribed above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic

which represents an epimeric mixture of the racemic compounds of formulaIa (syn) and Ib (anti), wherein the ratio of the racemic compound offormula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV), to the racemic compound offormula Ib (anti), which represents a racemic mixture of the singleenantiomers of formulae I_(V) and I_(VI), is from 1000:1 to 1:1000; andone component B) as described above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ia (syn), which represents a racemic mixtureof the single enantiomers of formulae I_(III) and I_(IV), is from 80 to99% by weight, preferrably 85 to 90% by weight; and one component B) asdescribed above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ib (anti), which represent a racemic mixtureof the single enantiomers of formulae I_(V) and I_(VI), is from 60 to99% by weight, preferrably 64 to 70% by weight; and one component B) asdescribed above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound of theformula I, wherein R₁ is difluoromethyl and R₂ is hydrogen; and onecomponent B) as described above. Within this embodiment of the presentinvention compounds of formula I occur in two enantiomeric forms, whichare described as the single enantiomers of formulae I_(VII) andI_(VIII):

The invention covers all such single enantiomers and mixtures thereof inany ratio.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a single enantiomerof formula I_(VII); and one component B) as described above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a single enantiomerof formula I_(VIII); and one component B) as described above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Id

which represents a mixture of the single enantiomers of formulae I_(VII)and I_(VIII),wherein the ratio of the single enantiomer of formula I_(VII) to thesingle enantiomer of formula I_(VIII) is from 1000:1 to 1:1000; and onecomponent B) as described above.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound of theformula I, wherein Y is

and R₁ is difluoromethyl; and one component B) as described above.Within this embodiment of the present invention compounds of formula Ioccur in two enantiomeric forms, which are described as the singleenantiomers of formulae I_(IX) and I_(X):

The invention covers all such single enantiomers and mixtures thereof inany ratio.

According to the instant invention, a “racemic mixture” of twoenantiomers or a “racemic compound” means a mixture of two enantiomersin a ratio of substantially 50:50 of the two single enantiomers.

Preferred components B) are selected from the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin;trifloxystrobin; and a compound of formula B-6;

an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil; an anilino-pyrimidine fungicide, selectedfrom the group consisting of cyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

Preferred components B) are selected from the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andChlorothalonil.

A more preferred component B) is azoxystrobin; picoxystrobin;cyproconazole; difenoconazole; propiconazole; fludioxonil; cyprodinil;fenpropimorph; fenpropidin; a compound of formula F-1; a compound offormula B-1; chlorothalonil, epoxiconazole or prothioconazole.

A further more preferred component B) is azoxystrobin; picoxystrobin;cyproconazole; difenoconazole; propiconazole; fludioxonil; cyprodinil;fenpropimorph; fenpropidin; a compound of formula F-1 or chlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and one component B) selected from thegroup consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin;trifloxystrobin; and a compound of formula B-6;

an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil; an anilino-pyrimidine fungicide, selectedfrom the group consisting of cyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and R₂ is C₁-C₆alkyl, and one component B)selected from the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin;trifloxystrobin; and a compound of formula B-6;

an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil; an anilino-pyrimidine fungicide, selectedfrom the group consisting of cyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl, Y is —CHR₂— and R₂ is isopropyl; and onecomponent B) selected from the group consisting of a strobilurinfungicide, selected from the group consisting of azoxystrobin,dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin,orysastrobin, picoxystrobin, pyraclostrobin; trifloxystrobin; and acompound of formula B-6;

an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil;an anilino-pyrimidine fungicide, selected from the group consisting ofcyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic

which represents an epimeric mixture of the racemic compounds of formulaIa (syn) and Ib (anti), wherein the ratio of the racemic compound offormula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV), to the racemic compound offormula Ib (anti), which represents a racemic mixture of the singleenantiomers of formulae I_(V) and I_(VI), is from 1000:1 to 1:1000; andone component B) selected from the group consisting of a strobilurinfungicide, selected from the group consisting of azoxystrobin,dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin,orysastrobin, picoxystrobin, pyraclostrobin; trifloxystrobin; and acompound of formula B-6;an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil; an anilino-pyrimidine fungicide, selectedfrom the group consisting of cyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

A further preferred embodiment of the present invention is representedby those combinations which comprise component A) a compound of formulaIc, which represents an epimeric mixture of the racemic compounds offormula Ia (syn) and Ib (anti), wherein the content of the racemiccompound of formula Ia (syn), which represents a racemic mixture of thesingle enantiomers of formulae I_(III) and I_(IV), is from 80 to 99% byweight, preferrably 85 to 90% by weight; and one component B) selectedfrom the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl,metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin;trifloxystrobin; and a compound of formula B-6;

an azole fungicide, selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole,ipconazole, metconazole, myclobutanil, oxpoconazole, pefurazoate,penconazole, prochloraz, propiconazole, prothioconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole, diclobutrazol, etaconazole, furconazole, furconazole-cisand quinconazole;a phenyl pyrrole fungicide, selected from the group consisting offenpiclonil and fludioxonil;an anilino-pyrimidine fungicide, selected from the group consisting ofcyprodinil, mepanipyrim and pyrimethanil;a morpholine fungicide, selected from the group consisting of aldimorph,dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;piperalin and a compound of formula B-7;a compound of formula F-1; a compound of formula B-1; chlorothalonil;famoxadone; fenamidone; acibenzolar-5-methyl; benalaxyl; benalaxyl-M;benomyl; bitertanol; boscalid; carboxin; carpropamid; copper;cyazofamid; cymoxanil; diethofencarb; dithianon; fenhexamide;fenoxycarb; fluazinam; flutolanil; folpet; guazatine; hymexazole;iprodione; lufenuron; mancozeb; metalaxyl; mefenoxam; metrafenone;nuarimol; paclobutrazol; pencycuron; penthiopyrad; procymidone;pyroquilon; quinoxyfen; silthiofam; sulfur; thiabendazole; thiram;triazoxide; tricyclazole; abamectin; emamectin benzoate; tefluthrin andthiamethoxam.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and one component B) selected from thegroup consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and R₂ is C₁-C₆alkyl, and one component B)selected from the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl, Y is —CHR₂— and R₂ is isopropyl; and onecomponent B) selected from the group consisting of a strobilurinfungicide, selected from the group consisting of azoxystrobin,fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic

which represents an epimeric mixture of the racemic compounds of formulaIa (syn) and Ib (anti), wherein the ratio of the racemic compound offormula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV), to the racemic compound offormula Ib (anti), which represents a racemic mixture of the singleenantiomers of formulae I_(V) and I_(VI), is from 1000:1 to 1:1000; andone component B) selected from the group consisting ofa strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise component A) a compound of formulaIc, which represents an epimeric mixture of the racemic compounds offormula Ia (syn) and Ib (anti), wherein the content of the racemiccompound of formula Ia (syn), which represents a racemic mixture of thesingle enantiomers of formulae I_(III) and I_(IV), is from 80 to 99% byweight, preferrably 85 to 90% by weight; and one component B) selectedfrom the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ib (anti), which represent a racemic mixtureof the single enantiomers of formulae I_(V) and I_(VI), is from 60 to99% by weight, preferrably 64 to 70% by weight; and one component B)selected from the group consisting of

a strobilurin fungicide, selected from the group consisting ofazoxystrobin, fluoxastrobin, picoxystrobin and pyraclostrobin;

an azole fungicide, selected from the group consisting of cyproconazole,difenoconazole, epoxiconazole, flutriafol, metconazole, propiconazole,prothioconazole, tetraconazole; fludioxonil, cyprodinil, fenpropimorph,fenpropidin, a compound of formula F-1; a compound of formula B-1 andchlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and one component B) selected from thegroup consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1; a compound of formula B-1; chlorothalonil,epoxiconazole and prothioconazole.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and R₂ is C₁-C₆alkyl, and one component B)selected from the group consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1; a compound of formula B-1; chlorothalonil,epoxiconazole and prothioconazole.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl, Y is —CHR₂— and R₂ is isopropyl; and onecomponent B) selected from the group consisting of azoxystrobin;picoxystrobin; cyproconazole; difenoconazole; propiconazole;fludioxonil; cyprodinil; fenpropimorph; fenpropidin; a compound offormula F-1; a compound of formula B-1; chlorothalonil, epoxiconazoleand prothioconazole.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic

which represents an epimeric mixture of the racemic compounds of formulaIa (syn) and Ib (anti), wherein the ratio of the racemic compound offormula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV), to the racemic compound offormula Ib (anti), which represents a racemic mixture of the singleenantiomers of formulae I_(V) and I_(VI), is from 1000:1 to 1:1000; andone component B) selected from the group consisting of azoxystrobin;picoxystrobin; cyproconazole; difenoconazole; propiconazole;fludioxonil; cyprodinil; fenpropimorph; fenpropidin; a compound offormula F-1; a compound of formula B-1; chlorothalonil, epoxiconazoleand prothioconazole.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ia (syn), which represents a racemic mixtureof the single enantiomers of formulae I_(III) and I_(IV), is from 80 to99% by weight, preferrably 85 to 90% by weight; and one component B)selected from the group consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1; a compound of formula B-1; chlorothalonil,epoxiconazole and prothioconazole.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ib (anti), which represent a racemic mixtureof the single enantiomers of formulae I_(V) and I_(VI), is from 60 to99% by weight, preferrably 64 to 70% by weight; and one component B)selected from the group consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1; a compound of formula B-1; chlorothalonil,epoxiconazole and prothioconazole.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and one component B) selected from thegroup consisting of

Azoxystrobin; Picoxystrobin; Cyproconazole; Difenoconazole;Propiconazole; Fludioxonil; Cyprodinil; Fenpropimorph; Fenpropidin; acompound of formula F-1 and Chlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl; and R₂ is C₁-C₆alkyl, and one component B)selected from the group consisting of

Azoxystrobin; Picoxystrobin; Cyproconazole; Difenoconazole;Propiconazole; Fludioxonil; Cyprodinil; Fenpropimorph; Fenpropidin; acompound of formula F-1 and Chlorothalonil.

A preferred embodiment of the present invention is represented by thosecombinations which comprise as component A) a compound of the formula I,wherein R₁ is difluoromethyl, Y is —CHR₂— and R₂ is isopropyl; and onecomponent B) selected from the group consisting of azoxystrobin;picoxystrobin; cyproconazole; difenoconazole; propiconazole;fludioxonil; cyprodinil; fenpropimorph; fenpropidin; a compound offormula F-1 and chlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise component A) a compound of formulaIc

which represents an epimeric mixture of the racemic compounds of formulaIa (syn) and Ib (anti), wherein the ratio of the racemic compound offormula Ia (syn), which represents a racemic mixture of the singleenantiomers of formulae I_(III) and I_(IV), to the racemic compound offormula Ib (anti), which represents a racemic mixture of the singleenantiomers of formulae I_(V) and I_(VI), is from 1000:1 to 1:1000; andone component B) selected from the group consisting ofazoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1 and chlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ia (syn), which represents a racemic mixtureof the single enantiomers of formulae I_(III) and I_(IV), is from 80 to99% by weight, preferrably 85 to 90% by weight; and one component B)selected from the group consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1 and chlorothalonil.

A further preferred embodiment of the present invention is representedby those combinations which comprise as component A) a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the content of theracemic compound of formula Ib (anti), which represent a racemic mixtureof the single enantiomers of formulae I_(V) and I_(VI), is from 60 to99% by weight, preferrably 64 to 70% by weight; and one component B)selected from the group consisting of

azoxystrobin; picoxystrobin; cyproconazole; difenoconazole;propiconazole; fludioxonil; cyprodinil; fenpropimorph; fenpropidin; acompound of formula F-1 and chlorothalonil.

In another embodiment of the invention, a preferred component B) isproquinazid; captan; a compound of formula B-2; a compound of formulaB-3; a compound of formula B-4; a compound of formula B-8; a compound offormula B-9;

a racemic compound of formula F-7 (trans); racemic compound of formulaF-8 (cis); a compound of formula F-9;

trinexapac-ethyl; chlormequat chloride; ethephon; mepiquat chloride;

a compound of formula A-1; a compound of formula A-2; a compound offormula A-3; a compound of formula A-4; a compound of formula A-5; acompound of formula A-6; a compound of formula A-7; a compound offormula A-8; a compound of formula A-9; a compound of formula A-10; acompound of formula A-11; a compound of formula A-12; a compound offormula A-13; a compound of formula A-14; a compound of formula A-15; acompound of formula A-15A; a compound of formula A-16; a compound offormula A-17; a compound of formula A-18; a compound of formula A-19; acompound of formula A-20; a compound of formula A-21; a compound offormula A-22; a compound of formula A-23; a compound of formula A-24; acompound of formula A-25; or a compound of formula A-26.

Within this embodiment, a further preferred component B) is proquinazid;captan; a compound of formula B-2; a compound of formula B-3; a compoundof formula B-4; a compound of formula B-8; a compound of formula B-9;

a racemic compound of formula F-7 (trans); racemic compound of formulaF-8 (cis); a compound of formula F-9;

trinexapac-ethyl; chlormequat chloride; ethephon; mepiquat chloride;

a compound of formula A-10 or a compound of formula A-23.

Within this embodiment, an even further preferred component B) is acompound of formula B-3 or a compound of formula A-10.

Within this embodiment, a further preferred embodiment of the presentinvention is represented by those combinations which comprise ascomponent A) a compound of the formula I, wherein R₁ is difluoromethyl,Y is —CHR₂— and R₂ is isopropyl; and one component B) selected from thegroup consisting of proquinazid; captan; a compound of formula B-2; acompound of formula B-3; a compound of formula B-4; a compound offormula B-8; a compound of formula B-9; a racemic compound of formulaF-7 (trans); racemic compound of formula F-8 (cis); a compound offormula F-9;

trinexapac-ethyl; chlormequat chloride; ethephon; mepiquat chloride;

a compound of formula A-1; a compound of formula A-2; a compound offormula A-3; a compound of formula A-4; a compound of formula A-5; acompound of formula A-6; a compound of formula A-7; a compound offormula A-8; a compound of formula A-9; a compound of formula A-10; acompound of formula A-11; a compound of formula A-12; a compound offormula A-13; a compound of formula A-14; a compound of formula A-15; acompound of formula A-15A; a compound of formula A-16; a compound offormula A-17; a compound of formula A-18; a compound of formula A-19; acompound of formula A-20; a compound of formula A-21; a compound offormula A-22; a compound of formula A-23; a compound of formula A-24; acompound of formula A-25; and a compound of formula A-26.

Within this embodiment, a further preferred embodiment of the presentinvention is represented by those combinations which comprise ascomponent A) a compound of the formula I, wherein R₁ is difluoromethyl,Y is —CHR₂— and R₂ is isopropyl; and one component B) selected from thegroup consisting of proquinazid; captan; a compound of formula B-2; acompound of formula B-3; a compound of formula B-4; a compound offormula B-8; a compound of formula B-9; a racemic compound of formulaF-7 (trans); racemic compound of formula F-8 (cis); a compound offormula F-9;

trinexapac-ethyl; chlormequat chloride; ethephon; mepiquat chloride;

a compound of formula A-10 and a compound of formula A-23.

Within this embodiment, a further preferred embodiment of the presentinvention is represented by those combinations which comprise ascomponent A) a compound of the formula I, wherein R₁ is difluoromethyl,Y is —CHR₂— and R₂ is isopropyl; and one component B) selected from thegroup consisting of a compound of formula B-3 and a compound of formulaA-10.

The active ingredient combinations are effective against harmfulmicroorganisms, such as microorganisms, that cause phytopathogenicdiseases, in particular against phytopathogenic fungi and bacteria.

The active ingredient combinations are effective especially againstphytopathogenic fungi belonging to the following classes: Ascomycetes(e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella,Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia,Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also knownas Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhynchosporium,Fusarium, Septoria, Cercospora, Alternaria, Pyricularia andPseudocercosporella); Oomycetes (e.g. Phytophthora, Peronospora,Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora,Plasmopara).

According to the invention “useful plants” typically comprise thefollowing species of plants: grape vines; cereals, such as wheat,barley, rye or oats; beet, such as sugar beet or fodder beet; fruits,such as pomes, stone fruits or soft fruits, for example apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries orblackberries; leguminous plants, such as beans, lentils, peas orsoybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers,coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants,such as marrows, cucumbers or melons; fibre plants, such as cotton,flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit ormandarins; vegetables, such as spinach, lettuce, asparagus, cabbages,carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceae,such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee;sugar cane; tea; vines; hops; durian; bananas; natural rubber plants;turf or ornamentals, such as flowers, shrubs, broad-leaved trees orevergreens, for example conifers. This list does not represent anylimitation.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors) as a result of conventional methodsof breeding or genetic engineering. An example of a crop that has beenrendered tolerant to imidazolinones, e.g. imazamox, by conventionalmethods of breeding (mutagenesis) is Clearfield® summer rape (Canola).Examples of crops that have been rendered tolerant to herbicides orclasses of herbicides by genetic engineering methods include glyphosate-and glufosinate-resistant maize varieties commercially available underthe trade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, forexample, insecticidal proteins, for example insecticidal proteins fromBacillus cereus or Bacillus popliae; or insecticidal proteins fromBacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c),CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, orvegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsine inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

In the context of the present invention there are to be understood byδ-endotoxins, for example CryIA(b), CryIA(c), CryIF, CryIF(a2),CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c, or vegetative insecticidalproteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly alsohybrid toxins, truncated toxins and modified toxins. Hybrid toxins areproduced recombinantly by a new combination of different domains ofthose proteins (see, for example, WO 02/15701). An example for atruncated toxin is a truncated CryIA(b), which is expressed in the Bt11maize from Syngenta Seed SAS, as described below. In the case ofmodified toxins, one or more amino acids of the naturally occurringtoxin are replaced. In such amino acid replacements, preferablynon-naturally present protease recognition sequences are inserted intothe toxin, such as, for example, in the case of CryIIIA055, acathepsin-D-recognition sequence is inserted into a CryIIIA toxin (seeWO 03/018810)

Examples of such toxins or transgenic plants capable of synthesisingsuch toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278,WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. CryI-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGardRootworm® (maize variety that expresses a CryIIIB(b1) toxin); YieldGardPlus® (maize variety that expresses a CryIA(b) and a CryIIIB(b1) toxin);Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I®(maize variety that expresses a CryIF(a2) toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a CryIA(c) toxin); Bollgard I® (cotton variety that expressesa CryIA(c) toxin); Bollgard II® (cotton variety that expresses aCryIA(c) and a CryIIA(b) toxin); VIPCOT® (cotton variety that expressesa VIP toxin); NewLeaf® (potato variety that expresses a CryIIIA toxin);NatureGard® and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/196105110. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated CryIA(b) toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/196105110. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a CryIA(b) toxin. Bt176 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCryIIIA toxin. This toxin is Cry3A055 modified by insertion of acathepsin-D-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/0219. MON 863expresses a CryIIIB(b1) toxin and has resistance to certain Coleopterainsects.5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96102.6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein CryIF for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a CryIA(b) toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer. Transgenic cropsof insect-resistant plants are also described in BATS (Zentrum fürBiosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058Basel, Switzerland) Report 2003, (http://bats.ch).

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

Antipathogenic substances which can be expressed by such transgenicplants include, for example, ion channel blockers, such as blockers forsodium and calcium channels, for example the viral KP1, KP4 or KP6toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases;the so-called “pathogenesis-related proteins” (PRPs; see e.g. EP-A-0 392225); antipathogenic substances produced by microorganisms, for examplepeptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818)or protein or polypeptide factors involved in plant pathogen defense(so-called “plant disease resistance genes”, as described in WO03/000906).

Useful plants of elevated interest in connection with present inventionare cereals; soybean; rice; oil seed rape; pome fruits; stone fruits;peanuts; coffee; tea; strawberries; turf; vines and vegetables, such astomatoes, potatoes, cucurbits and lettuce.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of a plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

A further aspect of the instant invention is a method of protectingnatural substances of plant and/or animal origin, which have been takenfrom the natural life cycle, and/or their processed forms against attackof fungi, which comprises applying to said natural substances of plantand/or animal origin or their processed forms a combination ofcomponents A) and B) in a synergistically effective amount.

According to the instant invention, the term “natural substances ofplant origin, which have been taken from the natural life cycle” denotesplants or parts thereof which have been harvested from the natural lifecycle and which are in the freshly harvested form. Examples of suchnatural substances of plant origin are stalks, leafs, tubers, seeds,fruits or grains. According to the instant invention, the term“processed form of a natural substance of plant origin” is understood todenote a form of a natural substance of plant origin that is the resultof a modification process. Such modification processes can be used totransform the natural substance of plant origin in a more storable formof such a substance (a storage good). Examples of such modificationprocesses are pre-drying, moistening, crushing, comminuting, grounding,compressing or roasting. Also falling under the definition of aprocessed form of a natural substance of plant origin is timber, whetherin the form of crude timber, such as construction timber, electricitypylons and barriers, or in the form of finished articles, such asfurniture or objects made from wood.

According to the instant invention, the term “natural substances ofanimal origin, which have been taken from the natural life cycle and/ortheir processed forms” is understood to denote material of animal originsuch as skin, hides, leather, furs, hairs and the like.

The combinations according the present invention can preventdisadvantageous effects such as decay, discoloration or mold.

A preferred embodiment is a method of protecting natural substances ofplant origin, which have been taken from the natural life cycle, and/ortheir processed forms against attack of fungi, which comprises applyingto said natural substances of plant and/or animal origin or theirprocessed forms a combination of components A) and B) in asynergistically effective amount.

A further preferred embodiment is a method of protecting fruits,preferably pomes, stone fruits, soft fruits and citrus fruits, whichhave been taken from the natural life cycle, and/or their processedforms, which comprises applying to said fruits and/or their processedforms a combination of components A) and B) in a synergisticallyeffective amount.

The combinations of the present invention may also be used in the fieldof protecting industrial material against attack of fungi. According tothe instant invention, the term “industrial material” denotes non-livematerial which have been prepared for use in industry. For example,industrial materials which are intended to be protected against attackof fungi can be glues, sizes, paper, board, textiles, carpets, leather,wood, constructions, paints, plastic articles, cooling lubricants,aqueous hydraulic fluids and other materials which can be infested with,or decomposed by, microorganisms. Cooling and heating systems,ventilation and air conditioning systems and parts of production plants,for example cooling-water circuits, which may be impaired bymultiplication of microorganisms may also be mentioned from amongst thematerials to be protected. The combinations according the presentinvention can prevent disadvantageous effects such as decay,discoloration or mold.

The combinations of the present invention may also be used in the fieldof protecting technical material against attack of fungi. According tothe instant invention, the term “technical material” includes paper;carpets; constructions; cooling and heating systems; ventilation and airconditioning systems and the like. The combinations according thepresent invention can prevent disadvantageous effects such as decay,discoloration or mold.

The combinations according to the present invention are particularlyeffective against powdery mildews; rusts; leafspot species; earlyblights and molds; especially against Septoria, Puccinia, Erysiphe,Pyrenophora and Tapesia in cereals; Phakopsora in soybeans; Hemileia incoffee; Phragmidium in roses; Alternaria in potatoes, tomatoes andcucurbits; Sclerotinia in turf, vegetables, sunflower and oil seed rape;black rot, red fire, powdery mildew, grey mold and dead arm disease invine; Botrytis cinerea in fruits; Monilinia spp. in fruits andPenicillium spp. in fruits.

The combinations according to the present invention are furthermoreparticularly effective against seedborne and soilborne diseases, such asAlternaria spp., Ascochyta spp., Botrytis cinerea, Cercospora spp.,Claviceps purpurea, Cochliobolus sativus, Colletotrichum spp., Epicoccumspp., Fusarium graminearum, Fusarium moniliforme, Fusarium oxysporum,Fusarium proliferatum, Fusarium solani, Fusarium subglutinans,Gaumannomyces graminis, Helminthosporium spp., Microdochium nivale,Phoma spp., Pyrenophora graminea, Pyricularia oryzae, Rhizoctoniasolani, Rhizoctonia cerealis, Sclerotinia spp., Septoria spp.,Sphacelotheca reilliana, Tilletia spp., Typhula incarnata, Urocystisocculta, Ustilago spp. or Verticillium spp.; in particular againstpathogens of cereals, such as wheat, barley, rye or oats; maize; rice;cotton; soybean; turf; sugarbeet; oil seed rape; potatoes; pulse crops,such as peas, lentils or chickpea; and sunflower.

The combinations according to the present invention are furthermoreparticularly effective against post harvest diseases such as Botrytiscinerea, Colletotrichum musae, Curvularia lunata, Fusarium semitecum,Geotrichum candidum, Monilinia fructicola, Monilinia fructigena,Monilinia laxa, Mucor piriformis, Penicilium italicum, Peniciliumsolitum, Penicillium digitatum or Penicillium expansum in particularagainst pathogens of fruits, such as pomefruits, for example apples andpears, stone fruits, for example peaches and plums, citrus, melons,papaya, kiwi, mango, berries, for example strawberries, avocados,pomegranates and bananas, and nuts.

The amount of a combination of the invention to be applied, will dependon various factors, such as the compounds employed; the subject of thetreatment, such as, for example plants, soil or seeds; the type oftreatment, such as, for example spraying, dusting or seed dressing; thepurpose of the treatment, such as, for example prophylactic ortherapeutic; the type of fungi to be controlled or the application time.

It has been found that the use of components B) in combination with thecompound of formula I surprisingly and substantially enhance theeffectiveness of the latter against fungi, and vice versa. Additionally,the method of the invention is effective against a wider spectrum ofsuch fungi that can be combated with the active ingredients of thismethod, when used solely.

The weight ratio of A):B) is so selected as to give a synergisticactivity. In general the weight ratio of A):B) is between 2000:1 and1:1000, preferably between 100:1 and 1:100, more preferably between 20:1and 1:50.

The synergistic activity of the combination is apparent from the factthat the fungicidal activity of the composition of A)+B) is greater thanthe sum of the fungicidal activities of A) and B).

The method of the invention comprises applying to the useful plants, thelocus thereof or propagation material thereof in admixture orseparately, a synergistically effective aggregate amount of a compoundof formula I and a compound of component B).

Some of said combinations according to the invention have a systemicaction and can be used as foliar, soil and seed treatment fungicides.

With the combinations according to the invention it is possible toinhibit or destroy the phytopathogenic microorganisms which occur inplants or in parts of plants (fruit, blossoms, leaves, stems, tubers,roots) in different useful plants, while at the same time the parts ofplants which grow later are also protected from attack byphytopathogenic microorganisms.

The combinations of the present invention are of particular interest forcontrolling a large number of fungi in various useful plants or theirseeds, especially in field crops such as potatoes, tobacco andsugarbeets, and wheat, rye, barley, oats, rice, maize, lawns, cotton,soybeans, oil seed rape, pulse crops, sunflower, coffee, sugarcane,fruit and ornamentals in horticulture and viticulture, in vegetablessuch as cucumbers, beans and cucurbits.

The combinations according to the invention are applied by treating thefungi, the useful plants, the locus thereof, the propagation materialthereof, the natural substances of plant and/or animal origin, whichhave been taken from the natural life cycle, and/or their processedforms, or the industrial materials threatened by fungus attack with acombination of components A) and B) in a synergistically effectiveamount.

The combinations according to the invention may be applied before orafter infection of the useful plants, the propagation material thereof,the natural substances of plant and/or animal origin, which have beentaken from the natural life cycle, and/or their processed forms, or theindustrial materials by the fungi.

The combinations according to the invention are particularly useful forcontrolling the following plant diseases: Alternaria species in fruitand vegetables, Ascochyta species in pulse crops, Botrytis cinerea instrawberries, tomatoes, sunflower, pulse crops, vegetables and grapes,Cercospora arachidicola in peanuts, Cochliobolus sativus in cereals,Colletotrichum species in pulse crops, Erysiphe species in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Fusariumspecies in cereals and maize, Gaumannomyces graminis in cereals andlawns, Helminthosporium species in maize, rice and potatoes, Hemileiavastatrix on coffee, Microdochium species in wheat and rye, Phakopsoraspecies in soybean, Puccinia species in cereals, broadleaf crops andperennial plants, Pseudocercosporella species in cereals, Phragmidiummucronatum in roses, Podosphaera species in fruits, Pyrenophora speciesin barley, Pyricularia oryzae in rice, Ramularia collo-cygni in barley,Rhizoctonia species in cotton, soybean, cereals, maize, potatoes, riceand lawns, Rhynchosporium secalis in barley and rye, Sclerotinia speciesin lawns, lettuce, vegetables and oil seed rape, Septoria species incereals, soybean and vegetables, Sphacelotheca reilliana in maize,Tilletia species in cereals, Uncinula necator, Guignardia bidwellii andPhomopsis viticola in vines, Urocystis occulta in rye, Ustilago speciesin cereals and maize, Venturia species in fruits, Monilinia species onfruits, Penicillium species on citrus and apples.

The combinations according to the invention are preventively and/orcuratively valuable active ingredients in the field of pest control,even at low rates of application, which have a very favorable biocidalspectrum and are well tolerated by warm-blooded species, fish andplants. The active ingredients according to the invention which arepartially known for their insecticidal action act against all orindividual developmental stages of normally sensitive, but alsoresistant, animal pests, such as insects or representatives of the orderAcarina. The insecticidal or acaricidal activity of the combinationsaccording to the invention can manifest itself directly, i.e. indestruction of the pests, which takes place either immediately or onlyafter some time has elapsed, for example during ecdysis, or indirectly,for example in a reduced oviposition and/or hatching rate, a goodactivity corresponding to a destruction rate (mortality) of at least 50to 60%.

Examples of the abovementioned animal pests are:

from the order Acarina, for example,

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp.,Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae,Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp.,Olygonychus pratensis, Ornithodoros spp., Panonychus spp.,Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp.,Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Tarsonemus spp.and Tetranychus spp.;from the order Anoplura, for example,Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. andPhylloxera spp.;from the order Coleoptera, for example,Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis,Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp.,Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorhoptrusspp., Melolontha spp., Orycaephilus spp., Otiorhynchus spp., Phlyctinusspp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae,Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. andTrogoderma spp.;from the order Diptera, for example,Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphoraerythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebraspp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilusspp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp.,Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoliaspp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletispomonella, Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. andTipula spp.;from the order Heteroptera, for example,Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp.,Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodniusspp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp.;from the order Homoptera, for example,Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp.,Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplasterspp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccushesperidum, Empoasca spp., Eriosoma larigerum, Erythroneura spp.,Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp.,Parlatoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp.,Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotusspp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphisspp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae andUnaspis citri;from the order Hymenoptera, for example,Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpiniapolytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprionspp., Solenopsis spp. and Vespa spp.;from the order Isoptera, for example,Reticulitermes spp.;from the order Lepidoptera, for example,Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabamaargillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp.,Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella,Carposina nipponensis, Chilo spp., Choristoneura spp., Clysiaambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp.,Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydiaspp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp.,Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp.,Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis,Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella,Lithocollethis spp., Lobesia botrana, Lymantria spp., Lyonetia spp.,Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp.,Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,Pectinophora gossypiela, Phthorimaea operculella, Pieris rapae, Pierisspp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp.,Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp.,Tortrix spp., Trichoplusia ni and Yponomeuta spp.;from the order Mallophaga, for example,Damalinea spp. and Trichodectes spp.;from the order Orthoptera, for example,Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae,Locusta spp., Periplaneta spp. and Schistocerca spp.;from the order Psocoptera, for example,Liposcelis spp.;from the order Siphonaptera, for example,Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;from the order Thysanoptera, for example,Frankliniella spp., Hercinothrips spp., Scirtothrips aurantii,Taeniothrips spp., Thrips palmi and Thrips tabaci;from the order Thysanura, for example,Lepisma saccharina;nematodes, for example root knot nematodes, stem eelworms and foliarnematodes; especially Heterodera spp., for example Heterodera schachtii,Heterodora avenae and Heterodora trifolii; Globodera spp., for exampleGlobodera rostochiensis; Meloidogyne spp., for example Meloidogyneincoginita and Meloidogyne javanica; Radopholus spp., for exampleRadopholus similis; Pratylenchus, for example Pratylenchus neglectansand Pratylenchus penetrans; Tylenchulus, for example Tylenchulussemipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus,Aphelenchoides and Anguina;crucifer flea beetles (Phyllotreta spp.);root maggots (Delia spp.) andcabbage seedpod weevil (Ceutorhynchus spp.).

The combinations according to the invention can be used for controlling,i.e. containing or destroying, animal pests of the abovementioned typewhich occur on useful plants in agriculture, in horticulture and inforests, or on organs of useful plants, such as fruits, flowers,foliage, stalks, tubers or roots, and in some cases even on organs ofuseful plants which are formed at a later point in time remain protectedagainst these animal pests.

When applied to the useful plants the compound of formula I is appliedat a rate of 5 to 2000 g a.i./ha, particularly 10 to 1000 g a.i./ha,e.g. 50, 75, 100 or 200 g a.i./ha, in association with 1 to 5000 ga.i./ha, particularly 2 to 2000 g a.i./ha, e.g. 100, 250, 500, 800,1000, 1500 g a.i./ha of a compound of component B), depending on theclass of chemical employed as component B).

In agricultural practice the application rates of the combinationaccording to the invention depend on the type of effect desired, andtypically range from 20 to 4000 g of total combination per hectare.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula I per kg of seed,preferably from 0.01 to 10 g per kg of seed, and 0.001 to 50 g of acompound of component B), per kg of seed, preferably from 0.01 to 10 gper kg of seed, are generally sufficient.

The invention also provides fungicidal compositions comprising acompound of formula I and a compound of component B) in asynergistically effective amount.

The composition of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the condensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula I together with acompound of component B), and optionally other active agents,particularly microbiocides or conservatives or the like. Concentratedforms of compositions generally contain in between about 2 and 80%,preferably between about 5 and 70% by weight of active agent.Application forms of formulation may for example contain from 0.01 to20% by weight, preferably from 0.01 to 5% by weight of active agent.Whereas commercial products will preferably be formulated asconcentrates, the end user will normally employ diluted formulations.

The Examples which follow serve to illustrate the invention, “activeingredient” denoting a mixture of compound I and a compound of componentB) in a specific mixing ratio.

FORMULATION EXAMPLES

Wettable powders a) b) c) active ingredient [I:comp B) = 1:3(a), 1:2(b),1:1(c)] 25% 50% 75% sodium lignosulfonate  5%  5% — sodium laurylsulfate  3% —  5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenolpolyethylene glycol ether —  2% — (7-8 mol of ethylene oxide) highlydispersed silicic acid  5% 10% 10% Kaolin 62% 27% —

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [I:comp B) =1:3(a), 1:2(b), 1:1(c)] 25% 50% 75% light mineral oil  5%  5%  5% highlydispersed silicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20

The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient (I:comp B) = 1:6) 10%octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide)  3%calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%

Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [I:comp B) =  5%  6%  4% 1:6(a),1:2(b), 1:10(c)] talcum 95% — — Kaolin — 94% — mineral filler — — 96%

Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient (I:comp B) = 2:1) 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%

The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient (I:comp B) = 1:10) 8% polyethyleneglycol (mol. wt. 200) 3% Kaolin 89% 

The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient (I:comp B) = 1:8) 40% propyleneglycol 10% nonylphenol polyethylene glycol ether (15 mol of ethyleneoxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1% siliconeoil (in the form of a 75% emulsion in water)  1% Water 32%

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient (I:comp B) =1:8) 40%  propylene glycol 5% copolymer butanol PO/EO 2%tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one0.5%   (in the form of a 20% solution in water) monoazo-pigment calciumsalt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water 45.3%  

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula I and a compound ofcomponent B), or of each of these compounds separately, are mixed with 2parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients.

The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

BIOLOGICAL EXAMPLES

A synergistic effect exists whenever the action of an active ingredientcombination is greater than the sum of the actions of the individualcomponents.

The action to be expected E for a given active ingredient combinationobeys the so-called COLBY formula and can be calculated as follows(COLBY, S. R. “Calculating synergistic and antagonistic responses ofherbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture

X=% action by active ingredient A) using p ppm of active ingredient

Y=% action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredientsA)+B) using p+q ppm of active ingredient is

$E = {X + Y - \frac{X \cdot Y}{100}}$

If the action actually observed (O) is greater than the expected action(E), then the action of the combination is super-additive, i.e. there isa synergistic effect. In mathematical terms the synergism factor SFcorresponds to O/E. In the agricultural practice an SF of ≧1.2 indicatessignificant improvement over the purely complementary addition ofactivities (expected activity), while an SF of ≦0.9 in the practicalapplication routine signals a loss of activity compared to the expectedactivity.

EXAMPLE B-1 Action Against Botrytis cinerea on Grapes

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 48-72 hrs. The fungicide interactionsin the combinations are calculated according to COLBY method.

Control of Botrytis cinerea Dosage in mg active ingredient/liter finalmedium Expected Observed Synergy control in control in Factor Cpd Ic inAzoxystrobin % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor 0.0222 — — 23 — 0.0074 —— 10 — 0.0025 — — 0 — — 1.80 — 14 — — 0.60 — 7 — 0.0222 1.80 34 54 1.60.0074 1.80 22 34 1.5 0.0025 1.80 14 27 1.9 0.0222 0.60 28 43 1.5 0.00740.60 16 31 1.9 0.0025 0.60  7 16 2.2 Expected Observed Synergy controlin control in Factor Cpd Ic in Prothioconazole % % SF = ppm in ppm (%C_(exp)) (% C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observedFactor — 0.2000 — 52 — — 0.0667 — 17 — — 0.0222 — 8 — 0.0667 — — 35 —0.0222 — — 18 — 0.0222 0.2000 60 94 1.5 Expected Observed Synergycontrol in control in Factor Cpd Ic in Picoxystrobin % % SF = ppm in ppm(% C_(exp)) (% C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expectedobserved Factor — 0.6000 — 20 — — 0.2000 — 12 — — 0.0667 — 6 — — 0.0222— 0 — 0.2000 — — 71 — 0.0667 — — 28 — 0.0222 — — 12 — 0.0222 0.6000 2988 3.0 0.0222 0.2000 22 88 4.0 0.0222 0.0667 17 85 4.9

In comparative examples B-1 to B-8 as component A) a specific compoundof formula Ic was used. Said compound of formula Ic was a compound offormula Ic, which represents an epimeric mixture of the racemiccompounds of formula Ia (syn) and Ib (anti), wherein the ratio of theracemic compound of formula Ia (syn), which represents a racemic mixtureof the single enantiomers of formulae I_(III) and I_(IV), to the racemiccompound of formula Ib (anti), which represents a racemic mixture of thesingle enantiomers of formula I_(V) and I_(VI), was 9:1.

b) Protective Treatment

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the grape plants are inoculated by spraying a sporesuspension (1×10⁶ conidia/ml) on the test plants. After an incubationperiod of 4 days at 21° C. and 95% relative humidity in a greenhouse thedisease incidence is assessed. The fungicide interactions in thecombinations are calculated according to COLBY method.

EXAMPLE B-2 Action Against Septoria tritici on Wheat

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 72 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

Control of Septoria tritici Expected Observed Synergy control in controlin Factor Cpd Ic in Propiconazole % % SF = ppm in ppm (% C_(exp)) (%C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observed Factor0.0008 — — 13 — 0.0001 — — 1 — — 0.067 — 7 — — 0.007 — 0 — 0.0008 0.06719 34 1.8 0.0001 0.007  1 8 6.4b) Protective Treatment

2 week old wheat plants cv. Riband are treated with the formulated testcompound (0.2% active ingredient) in a spray chamber. One day afterapplication, wheat plants are inoculated by spraying a spore suspension(10×10⁵ conidia/ml) on the test plants. After an incubation period of 1day at 23° C. and 95% relative humidity, the plants are kept for 16 daysat 23° C. and 60% relative humidity in a greenhouse. The diseaseincidence is assessed 18 days after inoculation. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-3 Action Against Pyricularia oryzae on Rice

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 72 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

Expected Observed Synergy control in control in Factor Cpd Ic inCyprodinil % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor Control of Pyriculariaoryzae Dosage in mg active ingredient/liter final medium 0.0222 — — 59 —0.0074 — — 33 — 0.0025 — — 13 — — 0.067 — 0 — — 0.007 — 0 — — 0.002 — 0— 0.0074 0.067 33 42 1.3 0.0074 0.007 33 40 1.2 0.0074 0.002 33 41 1.3Expected Observed Synergy control in control in Factor Cpd Ic inChlorothalonil % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor Control of Pyriculariaoryzae Dosage in mg active ingredient/liter final medium 0.0222 — — 59 —0.0074 — — 33 — 0.0025 — — 13 — — 0.067 — 0 — — 0.007 — 0 — — 0.002 — 0— 0.0074 0.067 33 42 1.3 0.0074 0.007 33 40 1.2 0.0074 0.002 33 41 1.3Expected Observed Synergy control in control in Factor Cpd Ic inCyproconazole % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor Control of Pyriculariaoryzae 0.0025 — — 6 — 0.0008 — — 3 — 0.0001 — — 2 — — 0.200 — 0 — —0.022 — 0 — 0.0025 0.200 6 11 1.8 0.0008 0.200 3 9 3.2 0.0001 0.200 2 42.0 0.0025 0.022 6 16 2.7 0.0008 0.022 3 5 1.7 0.0001 0.022 2 3 1.2b) Protective Treatment

Rice leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-4 Action Against Alternaria solani (Early Blight)

a) Fungal Growth Assay

Conidia—harvested from a freshly grown colony—of the fungus weredirectly mixed into nutrient broth (PDB potato dextrose broth). Afterplacing a (DMSO) solution of the test compounds into a microtiter plate(96-well format) the nutrient broth containing the fungal spores wasadded. The test plates were incubated at 24° C. and the inhibition ofgrowth was determined photometrically after 48 hrs. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

Control of Alternaria solani Dosage in mg active ingredient/liter finalmedium Expected Observed Synergy control in control in Factor Cpd Ic inFludioxonil % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor 0.0074 — — 27 — 0.0025 —— 8 — — 0.067 — 24 — — 0.022 — 1 — 0.0074 0.067 44 62 1.4 0.0025 0.06730 45 1.5 0.0074 0.022 27 37 1.3 0.0025 0.022 9 11 1.3b) Protective Treatment

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (2×10⁵ conidia/ml) on the test plants. After an incubationperiod of 3 days at 20° C. and 95% relative humidity in a growth chamberthe disease incidence is assessed. The fungicide interactions in thecombinations are calculated according to COLBY method.

EXAMPLE B-5 Action Against Pyrenophora teres (Net Blotch)

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 48 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

Control of Pyrenophora teres Expected Observed Synergy control incontrol in Factor Cpd Ic in Cpd F-1 % % SF = ppm in ppm (% C_(exp)) (%C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observed Factor —16.2 — 6 — —  5.4 — 2 — 0.2000 — — 55 — 0.0667 — — 37 — 0.2000 16.2 5873 1.3 0.2000  5.4 56 72 1.3 0.0667 16.2 41 56 1.4 0.0667  5.4 38 57 1.5b) Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-6 Action Against Venturia inaequalis on Apple

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 144 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

Control of Venturia inaequalis Expected Observed Synergy control incontrol in Factor Cpd Ic in Cpd B-1 % % SF = ppm in ppm (% C_(exp)) (%C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observed Factor —0.0074 — 61 — — 0.0025 — 32 — — 0.0008 — 17 — 0.2000 — — 59 — 0.0667 — —18 — 0.0222 — — 6 — 0.0667 0.0025 44 55 1.2 0.0667 0.0008 32 57 1.8Expected Observed Synergy control in control in Factor Cpd Ic inFenpropimorph % % SF = ppm in ppm (% C_(exp)) (% C_(obs)) % C_(obs)/%C_(exp) [mg/L] [mg/L] expected observed Factor — 0.0222 — 33 — — 0.0025— 0 — 0.0667 — — 18 — 0.0222 — — 10 — 0.0222 0.0222 39 53 1.3 0.02220.0025 10 33 3.4b) Protective Treatment

4 week old apple seedlings cv. McIntosh are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the apple plants are inoculated by spraying a sporesuspension (4×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 21° C. and 95% relative humidity the plants areplaced for 4 days at 21° C. and 60% relative humidity in a greenhouse.After another 4 day incubation period at 21° C. and 95% relativehumidity the disease incidence is assessed. The fungicide interactionsin the combinations are calculated according to COLBY method.

EXAMPLE B-7 Action Against Pythium ultimum (Damping Off)—Fungal GrowthAssay

Mycelial fragments of the fungus, prepared from a fresh liquid culture,were directly mixed into nutrient broth (PDB potato dextrose broth).After placing a (DMSO) solution of the test compounds into a microtiterplate (96-well format) the nutrient broth containing the fungal sporeswas added. The test plates were incubated at 24° C. and the inhibitionof growth was determined photometrically after 48 hrs. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

Control of Pythium ultimum Expected Observed Synergy control in controlin Factor Cpd Ic in Fenpropidin % % SF = ppm in ppm (% C_(exp)) (%C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observed Factor —16.2000 — 34 — —  5.4000 — 11 — 0.6000 — — 0 — 0.2000 — — 0 — 0.0667 — —0 — 0.2000 16.2000 34 48 1.4

EXAMPLE B-8 Action Against Leptosphaeria nodorum (Glume Blotch)—FungalGrowth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 48 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

Control of Leptosphaeria nodorum Expected Observed Synergy control incontrol in Factor Cpd Ic in Epoxiconazole % % SF = ppm in ppm (%C_(exp)) (% C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expected observedFactor — 0.0222 — 39 — — 0.0025 — 9 — 0.0667 — — 0 — 0.0222 — — 0 —0.0222 0.0222 39 91 2.3 0.0222 0.0025 9 21 2.3 Expected Observed Synergycontrol in control in Factor Cpd Ic in Difenoconazole % % SF = ppm inppm (% C_(exp)) (% C_(obs)) % C_(obs)/% C_(exp) [mg/L] [mg/L] expectedobserved Factor — 0.0074 — 73 — — 0.0025 — 16 — — 0.0008 — 5 — 0.2000 —— 0 — 0.0667 — — 0 — 0.2000 0.0025 16 88 5.5 0.2000 0.0008 5 74 13.80.0667 0.0025 16 21 1.3 0.0667 0.0008 5 10 1.8

EXAMPLE B-9 Action Against Pseudocercosporella herpotrichoides var.acuformis (Eyespot/Cereals)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 72 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

EXAMPLE B-10 Action Against Ustilago maydis (Corn Smut)—Fungal GrowthAssay

Conidia of the fungus from cryogenic storage were directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of the test compounds into a microtiter plate (96-well format)the nutrient broth containing the fungal spores was added. The testplates were incubated at 24° C. and the inhibition of growth wasdetermined photometrically after 48 hrs. The fungicide interactions inthe combinations are calculated according to COLBY method.

EXAMPLE B-11 Action Against Phytophthora infestans (Late Blight) onTomato—Protective Treatment

Tomato leaf disks are placed on water agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-12 Action Against Plasmopara viticola (Downy Mildew) on GrapeVines—Protective Treatment

Grape vine leaf disks are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 7 days afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-13 Action Against Botrytis cinerea (Grey Mould) onBeans—Protective Treatment

Bean leaf disks are placed on agar in multiwell plates (24-well format)and sprayed with test solutions. After drying, the leaf disks areinoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-14 Action Against Erysiphe graminis f.sp. hordei (BarleyPowdery Mildew) on Barley—Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-15 Action Against Erysiphe graminis f.sp. tritici (WheatPowdery Mildew) on Barley—Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-16 Action Against Puccinia recondita (Brown Rust) on Wheat

a) Protective Treatment of Leaf Segments

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 9 days afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

b) Protective Treatment of Plants

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (1×10⁵ uredospores/ml) on the test plants. After anincubation period of 2 days at 20° C. and 95% relative humidity theplants are kept in a greenhouse for 8 days at 20° C. and 60% relativehumidity. The disease incidence is assessed 10 days after inoculation.The fungicide interactions in the combinations are calculated accordingto COLBY method.

EXAMPLE B-17 Action Against Septoria nodorum on Wheat

a) Protective Treatment of Leaf Segments

Wheat leaf segments are placed on agar in multiwell plates (24-wellformat) and sprayed with test solutions. After drying, the leaf disksare inoculated with a spore suspension of the fungus. After appropriateincubation the activity of a compound is assessed 96 hrs afterinoculation as preventive fungicidal activity. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

b) Protective Treatment of Plants

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (5×10⁵ conidia/ml) on the test plants. After an incubationperiod of 1 day at 20° C. and 95% relative humidity the plants are keptfor 10 days at 20° C. and 60% relative humidity in a greenhouse. Thedisease incidence is assessed 11 days after inoculation. The fungicideinteractions in the combinations are calculated according to COLBYmethod.

EXAMPLE B-18 Action Against Podosphaera leucotricha (Powdery Mildew) onApple—Protective Treatment

5 week old apple seedlings cv. McIntosh are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter, the application apple plants are inoculated by shaking plantsinfected with apple powdery mildew above the test plants. After anincubation period of 12 days at 22° C. and 60% relative humidity under alight regime of 14/10 hours (light/dark) the disease incidence isassessed. The fungicide interactions in the combinations are calculatedaccording to COLBY method.

EXAMPLE B-19 Action Against Erysiphe graminis (Powdery Mildew) onBarley—Protective Treatment

1 week old barley plants cv. Regina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the barley plants are inoculated by shaking powdery mildewinfected plants above the test plants. After an incubation period of 6days at 20° C./18° C. (day/night) and 60% relative humidity in agreenhouse the disease incidence is assessed. The fungicide interactionsin the combinations are calculated according to COLBY method.

EXAMPLE B-20 Action Against Botrytis cinerea on Tomatoes—ProtectiveTreatment

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (1×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% relative humidity in a growth chamberthe disease incidence is assessed. The fungicide interactions in thecombinations are calculated according to COLBY method.

EXAMPLE B-21 Action Against Helminthosporium teres (Net Blotch) onBarley—Protective Treatment

1 week old barley plants cv. Regina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. Two days afterapplication, the barley plants are inoculated by spraying a sporesuspension (3×10⁴ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% relative humidity in a greenhouse thedisease incidence is assessed. The fungicide interactions in thecombinations are calculated according to COLBY method.

EXAMPLE B-22 Action Against Uncinula necator (Powdery Mildew) onGrapes—Protective Treatment

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the grape plants are inoculated by shaking plantsinfected with grape powdery mildew above the test plants. After anincubation period of 7 days at 26° C. and 60% relative humidity under alight regime of 14/10 hours (light/dark) the disease incidence isassessed. The fungicide interactions in the combinations are calculatedaccording to COLBY method.

The combinations according to the invention exhibit good activity in allof the above examples.

What is claimed is:
 1. A method of controlling phytopathogenic diseaseson useful plants or on propagation material thereof, which comprisesapplying to the useful plants, the locus thereof or propagation materialthereof a combination of components A) and B) in a synergisticallyeffective amount, wherein component A) is a compound of formula I

wherein R₁ is difluoromethyl, Y is —CHR₂—, and R₂ is isopropyl; or atautomer of such a compound; and component B) is a compound selectedfrom the group consisting of a triazole fungicide; prochloraz; acompound of formula B-1

chlorothalonil; fluazinam; dithianon; metrafenone; tricyclazole;mefenoxam; acibenzolar-S-methyl; and a compound of formula A10


2. A method according to claim 1, wherein component A) is a compound offormula Ic

which represents an epimeric mixture of racemic compounds of formula Ia(syn)

and racemic compounds of formula Ib (anti)


3. A method according to claim 2, wherein the racemic compound offormula Ia (syn) is present in an amount of from 80 to 99% by weight. 4.A method according to claim 1, wherein compound B) is a compound offormula B-1.
 5. A method of protecting natural substances of plant oranimal origin, which have been taken from the natural life cycle, ortheir processed forms, which comprises applying to the naturalsubstances of plant or animal origin or their processed forms acombination of components A) and B) in a synergistically effectiveamount, wherein component A) is a compound of formula I

wherein R₁ is difluoromethyl, Y is —CHR₂—, and R₇ is isopropyl; or atautomer of such a compound; and component B) is a compound selectedfrom the group consisting of a triazole fungicide; prochloraz; acompound of formula B-1

chlorothalonil; fluazinam; dithianon; metrafenone; tricyclazole;mefenoxam; acibenzolar-S-methyl; and a compound of formula A10


6. A fungicidal composition comprising a combination of components A)and B) in a synergistically effective amount, together with anagriculturally acceptable carrier, and optionally a surfactant, whereincomponent A) is a compound of formula I

wherein R₁ is difluoromethyl, Y is —CHR₂—, and R₂ is isopropyl; or atautomer of such a compound; and component B) is a compound selectedfrom the group consisting of a triazole fungicide; prochloraz; acompound of formula B-1

chlorothalonil; fluazinam; dithianon; metrafenone; tricyclazole;mefenoxam; acibenzolar-S-methyl; and a compound of formula A10


7. A fungicidal composition according to claim 6, wherein compound B) isa triazole fungicide selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,tricyclazole, triticonazole, diclobutrazol, etaconazole, furconazole,furconazole-cis and quinconazole.
 8. A fungicidal composition accordingto claim 7, wherein compound B) is a triazole fungicide selected fromthe group consisting of ipconazole, metconazole, penconazole,tebuconazole and tricyclazole.
 9. A fungicidal composition according toclaim 6, wherein compound B) is a compound of formula B-1.
 10. A methodaccording to claim 5, wherein compound B) is a compound of formula B-1.11. A method according to claim 5, wherein compound B) is a triazolefungicide selected from the group consisting of azaconazole,bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,tricyclazole, triticonazole, diclobutrazol, etaconazole, furconazole,furconazole-cis and quinconazole.
 12. A method according to claim 11,wherein compound B) is a triazole fungicide selected from the groupconsisting of ipconazole, metconazole, penconazole, tebuconazole andtricyclazole.
 13. A method according to claim 1, wherein compound B) isa triazole triazole fungicide selected from the group consisting ofazaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole,diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole,flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole,metconazole, myclobutanil, penconazole, propiconazole, prothioconazole,simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol,tricyclazole, triticonazole, diclobutrazol, etaconazole, furconazole,furconazole-cis and quinconazole.
 14. A method according to claim 13,wherein compound B) is a triazole fungicide selected from the groupconsisting of ipconazole, metconazole, penconazole, tebuconazole andtricyclazole.